TWI711649B - Fluoropolyether-containing polymer-modified silane, surface treating agent, and treated article - Google Patents

Abstract

A fluoropolyether-containing polymer-modified silane has general formula (1) wherein Rf is a monovalent fluorooxyalkyl or divalent fluorooxyalkylene-containing polymer residue, Y is a divalent to hexavalent hydrocarbon group which may have a silicon atom and/or a siloxane bond, W is a divalent to hexavalent hydrocarbon group which may have a silicon atom and/or a siloxane bond, R is independently an alkyl of 1 to 4 carbon atoms or phenyl, X is independently hydroxyl or a hydrolyzable group, the letters n, a and m are respectively integers from 1 to 3, 1 to 5 and 1 to 5, and α is 1 or 2. A surface treating agent containing this silane and/or a partial (hydrolytic) condensate thereof, when applied to an article, forms a coat of excellent water/oil repellency and abrasion resistance.

Description

Fluorine-containing polyether polymer modified silane, surface treatment agent and treated objects Cross reference of related applications

This non-provisional application is based on 35 U.S.C.§119(a) claiming the priority of the patent application number 2015-085708 filed in Japan on April 20, 2015, the full content of which is hereby incorporated for reference.

The present invention relates to a fluorine-containing polyether polymer modified silane. More specifically, the present invention relates to silane modified by a polymer containing fluorine polyether groups, which forms a film with excellent water repellency, oil repellency and wear resistance, and relates to containing silane and/or part thereof ( Hydrolysis) condensate surface treatment agent, and related to the surface treatment of the surface treatment agent.

Touch panel technology is now rapidly being adopted in mobile phone displays and other electronic device screens. However, the problem with the touch panel is that the screen is exposed, which creates many opportunities for direct contact with fingers, cheeks, etc., and can easily adhere to dirt (such as sebum). To improve the appearance As well as visibility, there is a growing demand for methods that make it more difficult for users to leave fingerprints on the display surface and easier to remove stains, leading to expectations for new materials that can meet these requirements. In particular, since fingerprints can be easily formed on the touch panel display, it is desirable to provide a water-repellent/oil-repellent coating on the display. Unfortunately, although the conventional water-repellent/oil-repellent coating has a high degree of water-repellency and oil-repellency and excellent dirt-wiping properties, the anti-smudge performance is reduced during use.

Compounds containing fluoropolyether groups have very low surface free energy and therefore generally have properties such as water repellency and oil repellency, chemical resistance, lubricity, mold release properties, and anti-smudge properties. These qualities are widely used in industries such as water/oil repellent antifouling agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision machinery, mold release agents, cosmetics and protective coatings. However, these same qualities also appear non-adhesive and non-adhesive to other substrate materials. Therefore, even when the compound can be applied to the substrate surface, it is challenging to induce the resulting coating to adhere to the substrate.

Related interest here is the silane coupling agent, which is similar to a substance that bonds the surface of a substrate (such as glass or fabric) with an organic compound and is widely used as a coating on the surface of various types of substrates. Silane coupling agents have organic functional groups and reactive silyl groups (usually hydrolyzable silyl groups, such as alkoxysilyl groups) on the same molecule. Partly due to the moisture in the air, the hydrolyzable silicon base causes a self-condensation reaction to form a film. The hydrolyzable silicon base in this film is chemically and physically bonded to the surface of glass, metal or the like, resulting in a strong and durable coating.

JP-A 2008-534696, JP-A 2008-537557, JP-A 2012-072272, JP-A 2012-157856 and JP-A 2013-136833 disclose the use of a fluorine-containing polyether polymer obtained by introducing a hydrolyzable silyl group to a compound containing a fluorine-containing polyether group The modified silane composition can form a coating that easily adheres to the substrate surface and gives the substrate surface water and oil repellency, chemical resistance, lubricity, mold release properties and anti-smudge properties.

The cured film on the lens or anti-reflective coating that is surface-treated by the polymer-modified silane composition obtained by introducing a hydrolyzable silyl group to a fluorine-containing polyether compound has Excellent lubricity and mold release properties. However, in comparison with cured films produced by vapor deposition, cured films produced by wet coating methods such as spray coating or dip coating cannot exhibit sufficient wear resistance.

Citation list

Patent Document 1: JP-A 2008-534696

Patent Document 2: JP-A 2008-537557

Patent Document 3: JP-A 2012-072272

Patent Document 4: JP-A 2012-157856

Patent Document 5: JP-A 2013-136833

Therefore, the object of the present invention is to provide a polymer-modified silane containing fluoropolyether, which can form a cured film with excellent water repellency, oil repellency and wear resistance, and to provide the silane and/or its part (hydrolyzed) Surface treatment of condensate Agents, and provide objects that have been surface-treated by surface treatment agents.

The inventor found that by using the polymer of the fluorine-containing polyether of the general formula (1) described later to modify the silane, the surface treatment agent containing the silane and/or its partial (hydrolysis) condensate can be formed with excellent A cured film with water and oil repellency and abrasion resistance.

其中Rf為含單價氟氧烷基或二價氟氧伸烷基之聚合物殘基，Y為可具有矽原子及/或矽氧烷鍵之二價至六價烴基團，W為可具有矽原子及/或矽氧烷鍵之二價至六價烴基團，R獨立為1至4個碳原子的烷基或苯基，X獨立為羥基或可水解基團，n為從1至3的整數，a為從1至5的整數，m為從1至5的整數，及α為1或2。 Accordingly, in one aspect, the present invention provides a fluoropolyether polymer modified silane having the general formula (1)

Wherein Rf is a polymer residue containing a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group, Y is a divalent to hexavalent hydrocarbon group that can have silicon atoms and/or siloxane bonds, and W is a polymer residue that can have silicon A divalent to hexavalent hydrocarbon group with atoms and/or siloxane bonds, R is independently an alkyl group or phenyl group with 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, and n is from 1 to 3 Integer, a is an integer from 1 to 5, m is an integer from 1 to 5, and α is 1 or 2.

In a preferred embodiment, in formula (1), α is 1 and Rf is part of general formula (2): F-(CF ₂ O) _p -(C ₂ F ₄ O) _q -( C ₃ F ₆ O) _r -(C ₄ F ₈ O) _s -C _d F _2d- (2) where p, q, r and s are integers from 0 to 200, and the sum is p+q+r+s =3 to 200, each repeating unit can be linear or branched, individual repeating units can be arranged arbitrarily, d is an integer from 1 to 3, and C _d F _2d units can be linear or branched.

In another preferred embodiment, in formula (1), α is 2 and Rf is a part of general formula (3): -C _d F _2d -O-(CF ₂ O) _p -(C ₂ F ₄ O) _q -(C ₃ F ₆ O) _r -(C ₄ F ₈ O) _s -C _d F _2d- (3) where p, q, r and s are integers from 0 to 200 respectively, the sum p+q+r+s=3 to 200, each repeating unit can be linear or branched, individual repeating units can be arranged arbitrarily, d is an integer from 1 to 3, and C _d F _2d units can be Straight or branched chain.

In formula (1), Y is preferably selected from the group consisting of: 3 to 10 carbon atoms of alkylene, 6 to 8 carbon atoms of arylalkylene of 2 to 8 carbon atoms Alkylene, a divalent group of an alkylene having 2 to 8 carbon atoms bonded to each other through a C ₁ -C ₄ silylene or C ₆ -C ₁₀ silylene structure, and a divalent group A divalent to tetravalent group of an alkylene having 2 to 10 carbon atoms bonded to the valence position on the tetravalent organopolysiloxane residue, the organopolysiloxane residue is linear and It has 2 to 10 silicon atoms or is branched or cyclic and has 3 to 10 silicon atoms.

In formula (1), W is preferably selected from the group consisting of: 2 to 10 carbon atoms of alkylene, 6 to 8 carbon atoms of arylalkylene of 2 to 8 carbon atoms Alkylene, an alkylene containing 2 to 6 carbon atoms of a diorganosilylene group, bonded to each other via a C ₁ -C ₄ silylene or C ₆ -C ₁₀ silylene structure, has 2 to The divalent group of an alkylene group with 8 carbon atoms and the divalent group of an alkylene group with 2 to 10 carbon atoms bonded at the valence position on the divalent to tetravalent organopolysiloxane residue To a tetravalent group, the organopolysiloxane residue is linear and has 2 to 10 silicon atoms or is branched or cyclic and has 3 to 10 silicon atoms.

In formula (1), each X can be independently selected from the group consisting of hydroxyl group, alkoxy group having 1 to 10 carbon atoms, alkoxy group having 2 to 10 carbon atoms, 1 to An oxy group of 10 carbon atoms, an alkenoxy group of 2 to 10 carbon atoms and a halogen group.

其中p1為從5至100的整數，q1為從5至100的整數，且總和p1+q1為從10至105的整數。 Preferred polymer-modified silanes of fluoropolyether include those of the following formula:

Where p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and the sum p1+q1 is an integer from 10 to 105.

In another aspect, the present invention provides a surface treatment agent containing polymer-modified silane and/or a partial (hydrolysis) condensate thereof.

In yet another aspect, the present invention provides an article surface-treated with the aforementioned surface treatment agent.

Advantageous effects of the invention

The polymer-modified silane of fluorine-containing polyether according to the present invention has improved substrate adhesion due to a large number of functional groups thereon. Therefore, the surface treatment of the surface treatment agent containing the polymer-modified silane and/or its partial (hydrolysis) condensate has excellent water/oil repellency and wear resistance.

Description of preferred implementation

The purpose, characteristics and advantages of the present invention will become more apparent from the following detailed description.

The polymer-modified silane of the fluorine-containing polyether of the present invention has the following general formula (1).

In formula (1), Rf is a polymer residue containing a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group, and Y is a divalent to hexavalent hydrocarbon group that may have a silicon atom and/or a siloxane bond , W is a divalent to hexavalent hydrocarbon group that may have silicon atoms and/or siloxane bonds, R is independently an alkyl group or phenyl group with 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n Is an integer from 1 to 3, a is an integer from 1 to 5, m is an integer from 1 to 5, and a is 1 or 2.

The silane of the present invention is a silane modified by a polymer containing a fluorine polyether group, and has a polymer residue (Rf) containing a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group and a hydrolyzable Silicon base (such as alkoxysilyl) or hydroxyl-containing silicon base (-Si(R) _3-n (X) _n ) is characterized by a structure in which the hydrocarbon chain Y and W are bonded. The presence of three or more reactive functional groups on the polymer gives the silane improved substrate adhesion and excellent wear resistance.

When α is 1, Rf is preferably a monovalent fluorooxane of the following general formula (2) base.

F-(CF ₂ O) _p -(C ₂ F ₄ O) _q -(C ₃ F ₆ O) _r -(C ₄ F ₈ O) _s -C _d F _2d- (2) Here, p, q , R and s are integers from 0 to 200, and the sum is p+q+r+s=3 to 200. Each repeating unit can be linear or branched, and individual repeating units can be arranged arbitrarily, d is from An integer of 1 to 3, and the C _d F _2d unit may be linear or branched.

When α is 2, Rf is preferably a divalent fluorooxyalkylene group of the following general formula (3).

-C _d F _2d -O-(CF ₂ O) _p -(C ₂ F ₄ O) _q -(C ₃ F ₆ O) _r -(C ₄ F ₈ O) _s -C _d F _2d- (3) Here, p, q, r and s are integers from 0 to 200, and the sum is p+q+r+s=3 to 200. Each repeating unit can be linear or branched, and individual repeating units can be Arbitrary arrangement, d is an integer from 1 to 3, and the C _d F _2d unit can be linear or branched.

In formulas (2) and (3), p, q, r, and s are integers from 0 to 200, respectively. Preferably, p is an integer from 5 to 100, q is an integer from 5 to 100, r is an integer from 0 to 100, and s is an integer from 0 to 100. The sum p+q+r+s=3 to 200, and preferably 10 to 100. Each repeating unit can be linear or branched, and individual repeating units can be arranged arbitrarily. More preferably, the sum p+q is an integer from 10 to 105, especially from 15 to 60, and r=s=0. It is desirable to have a sum p+q+r+s smaller than this upper limit because of good adhesion and curability, and it is desirable to have a sum larger than this lower limit because the characteristics of the fluoropolyether group can be fully exhibited.

In formulas (2) and (3), d is an integer from 1 to 3, and preferably 1 or 2. The C _d F _2d unit can be linear or branched.

Illustrative examples of Rf include the following.

-CF ₂ O(CF ₂ O) _p' CF ₂ --CF ₂ O(CF ₂ O) _p' (CF ₂ CF ₂ O) _q' CF ₂ --CF ₂ O(CF ₂ O) _p' (CF ₂ CF ₂ O) _q' (CF ₂ CF ₂ CF ₂ O) _r' CF ₂ --CF ₂ O(CF ₂ O) _p' (CF ₂ CF ₂ O) _q' (CF ₂ CF ₂ CF ₂ CF ₂ O) _s' CF ₂ --CF ₂ O(CF ₂ O) _p' (CF ₂ CF ₂ O) _q' (CF ₂ CF ₂ CF ₂ O) _r' (CF ₂ CF ₂ CF ₂ CF ₂ O) _s' CF ₂ --CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) _r' CF ₂ CF ₂ -

在此，p'、q'、r'和s'分別為1或更大的整數且具有與上文分別以p、q、r和s所指出之上限相同的上限。另外，u為從1至24的整數，且v為從1至24的整數。個別的重覆單元可任意排列。 _{F (CF 2 O) p '} CF 2 -F (CF 2 O) p' (CF 2 CF 2 O) q 'CF 2 -F (CF 2 O) p' (CF 2 CF 2 O) q '(CF _{2 CF 2 CF 2 O) r} 'CF 2 -F (CF 2 O) p' (CF 2 CF 2 O) q '(CF 2 CF 2 CF 2 CF 2 O) S' CF 2 -F (CF 2 O _{) p '(CF 2 CF 2} O) q' (CF 2 CF 2 CF 2 O) r '(CF 2 CF 2 CF 2 CF 2 O) s' CF 2 -F (CF 2 CF 2 O) q' CF _{2 -F (CF 2 CF 2 CF} 2 O) r 'CF 2 CF 2 -

_{-CF 2 O (CF 2 O)} p 'CF 2 --CF 2 O (CF 2 O) p' (CF 2 CF 2 O) q 'CF 2 --CF 2 O (CF 2 O) p' (CF _{2 CF 2 O) q '(} CF 2 CF 2 CF 2 O) r' CF 2 --CF 2 O (CF 2 O) p '(CF 2 CF 2 O) q' (CF 2 CF 2 CF 2 CF 2 _{O) s 'CF 2 --CF 2} O (CF 2 O) p' (CF 2 CF 2 O) q '(CF 2 CF 2 CF 2 O) r' (CF 2 CF 2 CF 2 CF 2 O) s _{'CF 2 --CF 2 CF 2 O} (CF 2 CF 2 CF 2 O) r' CF 2 CF 2 -

Here, p', q', r', and s'are each an integer of 1 or greater and have the same upper limit as the upper limit indicated by p, q, r, and s, respectively. In addition, u is an integer from 1 to 24, and v is an integer from 1 to 24. Individual repeating units can be arranged arbitrarily.

In the formula (1), Y is a divalent to hexavalent hydrocarbon group that may have a silicon atom and/or a siloxane bond, preferably divalent to tetravalent, and more preferably a divalent hydrocarbon group. The absence of low-bonding energy linkages (such as ether linkages) on the molecule can provide excellent wear-resistant coatings.

Illustrative examples of Y include alkylene groups of 3 to 10 carbon atoms, such as propylene group (trimethylene, methyl ethylene group), butylene group (tetramethylene, methyl propylene group), and hexamethylene group. Methylene; an alkylene group of 2 to 8 carbon atoms containing an arylene group of 6 to 8 carbon atoms, such as a phenylene group (for example, an alkylene group-arylene group of 8 to 16 carbon atoms); A divalent group of a C ₁ -C ₄ silylene or C ₆ -C ₁₀ silylene structure bonded to each other with 2 to 8 carbon atoms; and in the divalent to hexavalent organic poly The divalent to hexavalent group of alkylene having 2 to 10 carbon atoms bonded at the valence position on the siloxane residue, the organopolysiloxane residue is linear, branched or cyclic and It has 2 to 10, preferably 2 to 5 silicon atoms. Preferred examples include alkylene groups of 3 to 10 carbon atoms; alkylene groups of 2 to 6 carbon atoms containing phenylene groups; alkylene groups of 2 to 6 carbon atoms containing phenylene groups; alkylene groups of C ₁ -C ₄ or C ₆ -C ₁₀ A divalent group of an alkylene having 2 to 4 carbon atoms in which the aryl structure is bonded to each other; and a divalent group having 2 to 10 bonded at the valence position on the divalent to tetravalent organopolysiloxane residue A divalent to tetravalent group of an alkylene group with three carbon atoms, the organopolysiloxane residue is linear and has 2 to 10 silicon atoms or is branched or cyclic and has 3 to 10 silicon atoms. An alkylene having 3 to 6 carbon atoms is even more preferable.

The silylene structure and silyl aryl structure are exemplified by the following structures.

在此，可相同或不同的各R¹為1至4個碳原子的烷基(諸如甲基、乙基、丙基或丁基)或6至10個碳原子的芳基(諸如苯基)。R²為1至4個碳原子的伸烷基(諸如亞甲基、伸乙基、伸丙基(三亞甲基、甲基伸乙基))或6至10個碳原子的伸芳基(諸如伸苯基)。

Here, each R ¹ which may be the same or different is an alkyl group of 1 to 4 carbon atoms (such as methyl, ethyl, propyl, or butyl) or an aryl group of 6 to 10 carbon atoms (such as phenyl) . R ² is an alkylene group of 1 to 4 carbon atoms (such as methylene, ethylene group, propylidene (trimethylene, methyl ethylene group)) or an aryl group of 6 to 10 carbon atoms ( Such as phenylene).

The divalent to hexavalent organopolysiloxane residues that are linear, branched, or cyclic and have 2 to 10, preferably 2 to 5, silicon atoms are shown below as examples.

Here, R ¹ is as defined above, g is an integer from 1 to 9, preferably from 1 to 4, h is from 2 to 6, preferably an integer from 2 to 4, and j is from 0 to 8, preferably an integer of 0 or 1, the sum h+j is an integer from 3 to 10, preferably from 3 to 5, and k is an integer from 1 to 3, preferably 2 or 3.

Illustrative examples of Y include the following groups.

-CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2-

In formula (1), W is divalent to hexavalent, preferably divalent to tetravalent, and more preferably a divalent hydrocarbon group, and may have a silicon atom and/or siloxane key.

Illustrative examples of W include alkylene groups of 2 to 10 carbon atoms, such as ethylene group, propylene group (trimethylene, methyl ethylene group), butyl group (tetramethylene, methyl propylene group). Group) and hexamethylene; an alkylene group of 2 to 8 carbon atoms containing 6 to 8 carbon atoms, such as a phenylene group (for example, an alkylene group of 8 to 16 carbon atoms-arylene group Group); an alkylene group containing 2 to 6 carbon atoms of a diorganosilylene group, such as dimethylsilylene group or diethylsilylene group; via C ₁ -C ₄ silylene group or C ₆ -C _{10 A} divalent group of an alkylene having 2 to 8 carbon atoms bonded to each other in the silyl aryl structure; an alkylene having 2 to 6 carbon atoms of a divalent to hexavalent organopolysiloxane residue The organopolysiloxane residue is linear, branched or cyclic and has 2 to 10, preferably 2 to 5 silicon atoms; and on the divalent to hexavalent organopolysiloxane residue The divalent to hexavalent group of an alkylene having 2 to 10 carbon atoms bonded at the valence position of the organopolysiloxane residue is linear, branched or cyclic and has 2 to 10, Preferably it is 2 to 5 silicon atoms. Preferred examples include alkylene groups of 3 to 10 carbon atoms; alkylene groups of 2 to 6 carbon atoms containing phenylene groups; alkylene groups of 2 to 6 carbon atoms including dimethylsilylene group ; A divalent group of an alkylene having 2 to 4 carbon atoms bonded to each other via a C ₁ -C ₄ silylene or C ₆ -C ₁₀ silylene structure; including 2 to 10 silicon atoms Alkylene groups of 2 to 6 carbon atoms of linear divalent organopolysiloxane residues; and 2 to 10 bonded at valence positions on the divalent to tetravalent organopolysiloxane residues A divalent to tetravalent group of alkylene of carbon atoms, the organopolysiloxane residue is straight chain and has 2 to 10 silicon atoms or is branched or cyclic and has 3 to 10 silicon atoms. An alkylene having 3 to 6 carbon atoms is even more preferable.

Silane structure, silyl aryl structure, and divalent to hexavalent organopolysiloxane residues that are linear, branched or cyclic and have 2 to 10, preferably 2 to 5 silicon atoms The same method as above is an example.

Examples of W include the following groups.

-CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2-

In formula (1), each X is independently a hydroxyl group or a hydrolyzable group. X Illustrative examples include hydroxy; alkoxy of 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy; alkoxy of 2 to 10 carbon atoms An oxy group, such as methoxymethoxy and methoxyethoxy; an oxy group of 1 to 10 carbon atoms, such as acetoxy; an alkenoxy group of 2 to 10 carbon atoms, such as isopropenoxy Group; and halogen groups such as chlorine, bromine and iodine. Among them, methoxy, ethoxy, isopropenoxy and chlorine are preferred.

In formula (1), R is an alkyl group of 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, with methyl being preferred. Furthermore, n is an integer from 1 to 3, and 2 or 3 is preferable. From the viewpoint of reactivity and adhesion to the substrate, n is more preferably 3.

The subscript symbols "a" and "m" are integers from 1 to 5 respectively. When it is less than 1, the adhesion to the substrate is reduced, and when it is 6 or more, the number of terminal alkoxy groups becomes too high, which has an opposite effect on performance. Therefore, a and m are preferably from 1 to 3, and most preferably an integer of 1.

Examples of polymer-modified silanes of the fluorine-containing polyether of formula (1) are shown below. In each of these formulas, the repeating number (degree of polymerization) of each type of repeating unit constituting the fluorooxyalkyl group or the fluorooxyalkylene group may be any number satisfying the above formulas (2) and (3).

在此，p1為從5至100的整數，q1為從5至100的整數，且總和p1+q1為從10至105的整數。

Here, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and the sum p1+q1 is an integer from 10 to 105.

The polymer-modified silane of formula (1) in which α in formula (1) is 1 can be prepared, for example, by the following method.

In an exemplary method, a fluorooxyalkyl group-containing polymer having three or more olefin positions on one end of the molecular chain is dissolved in a solvent, usually a fluorocarbon solvent, such as 1,3-bis( Trifluoromethyl)benzene. The organosilicon compound (such as trimethoxysilane) with SiH group and terminal hydrolyzable group on the molecule is added to the solution and the reaction mixture is added to the hydrosilation catalyst (such as chloroplatinic acid/vinylsiloxane composite). In the presence of a toluene solution of the substance) at a temperature of 40 to 120°C, preferably 60 to 100°C, and more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, and more preferably Aging for about 24 hours.

In the preparation of the fluorine-containing poly of formula (1) in which α in formula (1) is 1 In another method of upgrading silane with ether polymers, a fluorooxyalkyl group-containing polymer having three or more olefin positions on one end of the molecular chain is dissolved in a solvent, usually a fluorocarbon solvent, such as 1,3-Bis(trifluoromethyl)benzene. An organosilicon compound (such as trichlorosilane) having SiH groups and terminal hydrolyzable groups on the molecule is added to the solution and the reaction mixture is exposed to a hydrosilation catalyst (such as chloroplatinic acid/vinylsiloxane composite). In the presence of the toluene solution) at a temperature of 40 to 120°C, preferably 60 to 100°C, and more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, and more preferably Aging in about 24 hours. The substituents on the silyl group are then converted into, for example, methoxy groups.

An organosilicon compound containing SiH groups without terminal hydrolyzable groups can be used instead of organosilicon compounds having SiH groups and terminal hydrolyzable groups on the molecule. In this example, an organosilicon compound having two or more SiH groups on the molecule and no terminal hydrolyzable group is used as the organosilicon compound. As in the above-mentioned method, the fluorooxyalkyl group-containing polymer having three or more olefin positions on one end of the molecular chain and the polymer having two or more SiH groups on the molecule and no terminal hydrolyzable groups The organosilicon compound reacts, and then becomes a mixture of a polymer with terminal SiH groups obtained as a reaction product and an organosilicon compound (such as allyltrimethoxysilane) having olefin positions and terminal hydrolyzable groups on the molecule In the presence of a hydrosilation catalyst (such as a toluene solution of chloroplatinic acid/vinylsiloxane complex) at a temperature of 40 to 120°C, preferably 60 to 100°C, and more preferably about 80°C It is aged for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours.

The fluorooxyalkyl group-containing polymer having three or more olefin positions at one end of the molecular chain is generally a fluorooxyalkyl group-containing polymer of the following general formula (4).

在此，Rf係如上文所定義，Z為二價烴基團，且V為二有機亞矽基、二價有機矽氧烷殘基或二價烴基團；烴基團可包括矽原子及/或矽氧烷鍵。字母b為0或1。

Here, Rf is as defined above, Z is a divalent hydrocarbon group, and V is a diorganosilylene group, a divalent organosiloxane residue or a divalent hydrocarbon group; the hydrocarbon group may include silicon atoms and/or silicon Oxane bond. The letter b is 0 or 1.

In formula (4), Z is a divalent hydrocarbon group. Preferably, the divalent hydrocarbon group has 1 to 8, and particularly 1 to 4 carbon atoms. Examples include alkylene groups of 1 to 8 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methyl ethylene), butyl (tetramethylene, methyl propylene) Group), hexamethylene and octamethylene; and alkylene groups containing 6 to 8 carbon atoms, such as phenylene groups (for example, alkylene-arylene groups of 7 to 8 carbon atoms) ). Z is preferably a linear alkylene group of 1 to 4 carbon atoms.

In formula (4), when b is 1, then V is a diorganosilylene group, a divalent organosiloxane residue or a divalent hydrocarbon group, and the hydrocarbon group may include a silicon atom and/or a siloxane bond .

Examples of V include divalent hydrocarbon groups of preferably 1 to 14 carbon atoms, and more preferably 1 to 10 carbon atoms, including alkylene groups of 1 to 8 carbon atoms, such as methylene, ethylene , Propylene (trimethylene, methyl ethylene), butyl (tetramethylene, methyl propylene), hexamethylene and octamethylene; and containing 6 to 8 carbon atoms The aryl alkylene (example Such as the alkylene group of 7 to 14 carbon atoms-arylene group); the alkylene group of 1 to 4 carbon atoms containing diorganosilylene, such as dimethylsilylene or diethylsilylene; two Organosilylene, such as dimethylsilyl or diethylsilyl; and divalent organosiloxane residues of 2 to 10 silicon atoms. V is preferably a linear alkylene group of 1 to 4 carbon atoms, an alkylene group of 1 to 4 carbon atoms containing a dimethylsilylene group, a dimethylsilylene group or a tetramethyldisiloxane Residues.

The divalent organopolysiloxane residue is the residue of the following formula as an example.

Here, R ¹ is as defined above. The subscript symbol g'is an integer from 1 to 9, and preferably 1 to 3.

Examples of V include the following groups.

-CH ₂ --CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH _2-

Preferred examples of the fluorooxyalkyl group-containing polymer of formula (4) include those The formula shown below. The repeating number (degree of polymerization) of each type of repeating unit constituting the fluorooxyalkyl group in each formula can be any number that satisfies Rf of formula (2).

在此，r1為從1至100的整數，且p1、q1及總和p1+q1係如上文所定義。

Here, r1 is an integer from 1 to 100, and p1, q1, and the sum p1+q1 are as defined above.

The fluorooxyalkyl group-containing polymer of formula (4) can be prepared by, for example, mixing a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain with an olefin introducing compound, and mixing the mixture with a base and In the presence of optional additives or solvents to improve reactivity, at a temperature of 0 to 90°C, preferably 60 to 80°C, and more preferably about 70°C, for 1 to 25 hours, preferably 3 to 10 Hours, and more preferably about 6 hours of aging.

In another method of preparing the fluorooxyalkyl group-containing polymer of formula (4), the dehydrogenation reaction is a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and an alkene-containing hydrosilane or In the presence of dehydrogenation catalysts and optionally used solvents between hydrosiloxanes, the temperature is 0 to 60°C, preferably 15 to 35°C, and more preferably about 25°C for 10 to 24 hours , Preferably 30 minutes to 2 hours, and more preferably about 1 hour.

Examples of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain used to prepare the fluorooxyalkyl group-containing polymer of formula (4) include those shown below.

在此，r1、p1、q1及總和p1+q1係如上文所定義。

Here, r1, p1, q1, and the sum p1+q1 are as defined above.

The fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain can be prepared, for example, by the following method: a polymer containing a fluorine group (-C(=O)-F) at one end of the molecular chain The perfluorooxyalkyl polymer is mixed with Grignard reagent as a nucleophilic reagent and a solvent (such as 1,3-bis(trifluoromethyl)benzene or tetrahydrofuran), and at 0 to 80°C, It is preferably 50 to 70°C, and more preferably about 60°C for 1 to 6 hours, preferably 3 to 5 hours, and more preferably about 4 hours of aging.

In addition to the above-mentioned fluorine, other groups can also be used as the group at one end of the molecular chain in the perfluorooxyalkyl group-containing polymer, such as halides, acid anhydrides, esters, carboxylic acids, and amides.

Examples of perfluorooxyalkyl group-containing polymers having such groups at one end of the molecular chain are shown below.

在此，p1、q1及總和p1+q1係如上文所定義。

Here, p1, q1, and the sum p1+q1 are as defined above.

Examples of nucleophilic reagents that can be used to prepare fluorooxyalkyl-containing polymers having a hydroxyl group at one end of the molecular chain include allyl magnesium halide, 3-butenyl magnesium halide, and 4-pentenyl magnesium halide And 5-hexenyl magnesium halide. It is also possible to use the corresponding lithium reagent.

The amount of nucleophilic agent used may be 2 to 5 equivalents per equivalent of reactive end groups on the perfluorooxyalkyl group-containing polymer, more preferably 2.5 to 3.5 equivalents, and even more preferably about 3 equivalent.

Examples of solvents that can be used to prepare the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain include the following fluorocarbon solvents: 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene , Hydrofluoroether (HFE) solvents (Novec series obtained from 3M Co.) (such as methyl nonafluorobutyl ether, methyl nine Fluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2 -(Trifluoromethyl)pentane), and perfluorinated solvents composed of fully fluorinated compounds (Fluorinert series obtained from 3M Co.). Other organic solvents that can be used include ether solvents such as tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxins. alkyl.

The amount of the solvent used may be 10 to 300 parts by weight per 100 parts by weight of the perfluorooxyalkyl group-containing polymer, preferably 100 to 200 parts by weight, and more preferably about 150 parts by weight.

Next, the reaction was stopped and the reaction mixture was separated into a water layer and a fluorocarbon solvent layer by a liquid separation operation. The fluorocarbon solvent layer thus obtained is washed with an organic solvent and the solvent is removed by distillation to give a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain.

Examples of olefin-introducing compounds that can be used to prepare the fluorooxyalkyl group-containing polymer of formula (4) include allyl halides such as allyl chloride, allyl bromide, and allyl iodide, and also include 4-chloro -1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 5-chloro-1-pentene, 5-bromo-1-pentene and 5-iodo-1-pentene .

The amount of the olefin-introducing compound used may be 1 to 10 equivalents, and more preferably 2.5 to 6 equivalents per equivalent of reactive end groups on the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain. And even more preferably about 5 equivalents.

The base series that can be used to prepare the fluorooxyalkyl group-containing polymer of formula (4) are exemplified by amines and alkali metal bases. Examples of amines include triethylamine, diisopropylethyl Amine, pyridine, DBU and imidazole. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, potassium tertiary butoxide, lithium diisopropylamide, lithium bis(trimethylsilyl)amide , Bis(trimethylsilyl) sodium and bis(trimethylsilyl) potassium.

The amount of base used may be 1 to 10 equivalents, more preferably 4 to 6 equivalents per equivalent of reactive end groups on the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain, and even More preferably, it is about 5 equivalents.

When preparing the fluorooxyalkyl group-containing polymer of formula (4), tetrabutylammonium halide, alkali metal halide, and the like can be used as additives to increase reactivity. Examples of such additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, and crown ether. These additives increase reactivity by catalytic halogen exchange with olefin-introduced compounds in the reaction system, and crown ethers increase reactivity by coordination with metals.

The amount of these additives used may be 0.005 to 0.1 equivalents, more preferably 0.01 to 0.05 equivalents per equivalent of reactive end groups on the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain, And even more preferably about 0.02 equivalent.

A solvent can be used to prepare the fluorooxyalkyl group-containing polymer of formula (4). The use of solvents is not absolutely necessary, but examples of solvents that can be used include the following fluorocarbon solvents: fluorine-containing aromatic hydrocarbon solvents (such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene) , Hydrofluoroether (HFE) solvents (Novec series obtained from 3M Co.) (such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3- Methoxy-2-(trifluoromethyl)pentane), and a perfluorinated solvent composed of fully fluorinated compounds (Fluorinert series obtained from 3M Co.). In addition, usable organic solvents include dimethylformamide, dimethylacetamide, dimethyl sulfenium, acetonitrile, and THF.

When a solvent is used, the amount of the solvent used can be 10 to 300 parts by weight, preferably 30 to 150 parts by weight per 100 parts by weight of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain, And more preferably about 50 parts by weight.

Examples of olefin-containing hydrosiloxanes and hydrosiloxanes that can be used to prepare the fluorooxyalkyl-containing polymer of formula (4) include hydrosiloxanes such as dimethylvinylsilane, dimethylallylsilane, di Ethyl vinyl silane and diethyl allyl silane; and hydrogen siloxanes such as vinyl tetramethyl disiloxane, allyl tetramethyl disiloxane, vinyl tetraethyl disiloxy Alkyl, allyl tetraethyl disiloxane, vinyl tetraphenyl disiloxane, allyl tetraphenyl disiloxane, vinyl hexamethyl trisiloxane and allyl hexamethyl Trisiloxane.

The amount of the olefin-containing hydrosiloxane and the hydrosiloxane may be used in an amount of 1 to 5 equivalents per equivalent of reactive end groups on the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain, and more It is preferably 1.5 to 3 equivalents, and even more preferably about 2 equivalents.

The dehydrogenation catalysts that can be used to prepare the fluorooxyalkyl group-containing polymer of formula (4) are based on rhodium, palladium, ruthenium and other platinum group metals, and boron catalysts are examples. Examples include catalysts based on platinum group metals, such as palladium (triphenylphosphine) and rhodium chloride (triphenylphosphine), and boron catalysts, such as (Pentafluorophenyl)borane.

The amount of the dehydrogenation catalyst used may be 0.01 to 0.0005 equivalents per equivalent of reactive end groups on the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain, more preferably 0.007 to 0.001 equivalents , And even more preferably about 0.005 equivalents.

Next, the reaction was stopped and the reaction mixture was separated into a water layer and a fluorocarbon solvent layer by a liquid separation operation. The fluorocarbon solvent layer thus obtained is washed with an organic solvent and the solvent is removed by distillation to give the fluorooxyalkyl group-containing polymer of formula (4).

In preparing the polymer-modified silane of the fluorine-containing polyether of formula (1) in which α is 1, the solvent used is preferably a fluorocarbon solvent. Illustrative examples of fluorocarbon solvents include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, hydrofluoroether (HFE) solvents (Novec series obtained from 3M Co.) (such as methyl nonafluoromethyl) Butyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether and 1,1,1,2,3,4,4,5,5,5-decafluoro-3 -Methoxy-2-(trifluoromethyl)pentane), and a perfluorinated solvent composed of fully fluorinated compounds (Fluorinert series obtained from 3M Co.).

The solvent can be used in an amount of 10 to 300 parts by weight, preferably 50 to 150 parts by weight per 100 parts by weight of the perfluorooxyalkyl group-containing polymer having three or more olefin positions on one end of the molecular chain , And more preferably about 100 parts by weight.

In preparing the polymer-modified silane of the fluorine-containing polyether of formula (1) in which α is 1, the organosilicon compound having SiH groups and terminal hydrolyzable groups in the molecule is preferably the following general formula (5) To any of (8) Compound.

在此，R、X、n、R¹、R²、g和j係如上文所定義。R³為2至8個碳原子的二價烴基團，i為從2至9的整數，較佳為2至4，且總和i+j為從2至9的整數。

Here, R, X, n, R ¹ , R ² , g, and j are as defined above. R ³ is a divalent hydrocarbon group of 2 to 8 carbon atoms, i is an integer from 2 to 9, preferably 2 to 4, and the sum i+j is an integer from 2 to 9.

Examples of the divalent hydrocarbon group R ³ having 2 to 8, preferably 2 or 3 carbon atoms include alkylene such as methylene, ethylene, propylene (trimethylene, methylethylene Group), butylene (tetramethylene, methyl propylene), hexamethylene, and octamethyl; arylene, such as phenyl; and two or more of these groups Combinations (e.g. alkylene-arylene). Among these, ethylene and trimethylene are preferred.

Examples of these organosilicon compounds having SiH groups and terminal hydrolyzable groups on the molecule include trimethoxysilane, triethoxysilane, tripropylene Oxysilane, triisopropoxysilane, tributoxysilane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane and silanes such as the following.

In the preparation of polymer-modified silane of fluorine-containing polyether of formula (1) in which α is 1, when one end of the molecular chain has three or more olefin positions on the fluorooxyalkyl group When reacting with organosilicon compounds with SiH groups and terminal hydrolyzable groups on the molecule, the amount of use of the organosilicon compounds with SiH groups and terminal hydrolyzable groups on the molecule is to be on one end of the molecular chain The fluorooxyalkyl group-containing polymer having three or more olefin positions preferably has 3 to 9 equivalents per equivalent of reactive end groups, more preferably 5 to 7 equivalents, and even more preferably about 6 equivalents .

In the preparation of polymer-modified silanes of fluorine-containing polyether of formula (1) in which α is 1, organosilicon compounds having two or more SiH groups on the molecule and no terminal hydrolyzable groups are preferred Is the following general formula (9) to (11) A compound of any one of them.

在此，R¹、R²、g、j和i係如上文所定義。

Here, R ¹ , R ² , g, j, and i are as defined above.

Examples of organosilicon compounds having two or more SiH groups on the molecule and no terminal hydrolyzable groups include those shown below.

In the preparation of polymer-modified silane of fluorine-containing polyether of formula (1) in which α is 1, when one end of the molecular chain has three or more olefin positions on the fluorooxyalkyl group When reacting with organosilicon compounds with two or more SiH groups and no terminal hydrolyzable groups on the molecule, they have two or more SiH groups on the molecule and no terminal hydrolyzable groups The amount of the organosilicon compound used is preferably 7 to 30 equivalents per equivalent of reactive end groups on the fluorooxyalkyl group-containing polymer having three or more olefin positions on one end of the molecular chain, It is more preferably 10 to 20 equivalents, and even more preferably about 15 equivalents.

In the preparation of polymer-modified silanes of fluorine-containing polyether of formula (1) in which α is 1, the organosilicon compound having olefin positions and terminal hydrolyzable groups on the molecule is preferably the following general formula (12) Compound.

In formula (12), R, X, and n are as defined above, and U is a single bond or a divalent hydrocarbon group of 1 to 6 carbon atoms. Examples of divalent hydrocarbon groups of 1 to 6 carbon atoms include alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene) , Methylidene) and hexamethylene, and phenylene. U is preferably a single bond or a methylene group.

In the preparation of polymer-modified silane of fluoropolyether of formula (1) where α is 1, when the organosilicon compound with olefin position and terminal hydrolyzable group on the molecule is on one end of the molecular chain The reaction product of a polymer with three or more olefin positions containing a fluorooxyalkyl group and an organosilicon compound with two or more SiH groups and no terminal hydrolyzable group on the molecule The amount of the organosilicon compound with olefin positions and terminal hydrolyzable groups is based on the fluorooxyalkyl group-containing polymer having three or more olefin positions on one end of the molecular chain and two or more molecules on the molecule. Multiple SiH groups and organosilicon compounds without terminal hydrolyzable groups The reactive end group per equivalent of the reaction product of the compound is preferably 3 to 9 equivalents, more preferably 5 to 7 equivalents, and even more preferably about 6 equivalents.

In the preparation of polymer-modified silane of fluorine-containing polyether of formula (1) where α is 1, the hydrosilation catalyst is a catalyst with platinum group metals as the substrate (such as platinum black, chloroplatinic acid, alcohol Modified chloroplatinic acid, chloroplatinic acid and compounds such as olefins, aldehydes, vinyl silicone or acetylene alcohol), palladium (triphenylphosphine) and rhodium chloride (triphenylphosphine) are examples. Platinum compounds are preferred, such as vinylsiloxane coordination compounds.

The usage amount of the hydrosilation catalyst with transition metal as the substrate is relative to the fluorooxyalkyl group-containing polymer with three or more olefin positions on one end of the molecular chain and two or more on the molecule The weight of the reaction product of a SiH group and an organosilicon compound without a terminal hydrolyzable group is preferably 0.1 to 100 ppm, and more preferably 1 to 50 ppm.

The target compound can then be obtained by distilling off the solvent and unreacted reagents under reduced pressure.

作為在分子鏈之一個末端上具有三或更多個烯烴位置的含氟氧烷基之聚合物及使用三甲氧基矽烷作為在分子上具有SiH基團及末端可水解基團之有機矽化合物可獲得下式化合物。 For example, by using a compound of the formula

As a polymer containing three or more olefin positions on one end of the molecular chain, and using trimethoxysilane as an organosilicon compound having SiH groups and terminal hydrolyzable groups on the molecule The compound of the following formula is obtained.

The polymer-modified silane of formula (1) in which α in formula (1) is 2 can be prepared, for example, by the following method.

In an exemplary method, the fluorooxyalkylene polymer having at least three olefin positions on the two ends of the molecular chain is dissolved in a solvent, usually a fluorocarbon solvent, such as 1,3-bis (Trifluoromethyl)benzene. The organosilicon compound (such as trimethoxysilane) with SiH group and terminal hydrolyzable group on the molecule is added to the solution and the reaction mixture is added to the hydrosilation catalyst (such as chloroplatinic acid/vinylsiloxane composite). In the presence of a toluene solution of the substance) at a temperature of 40 to 120°C, preferably 60 to 100°C, and more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, and more preferably Aging for about 24 hours.

Alternatively, an organosilicon compound having a SiH group and no terminal hydrolyzable group can be used instead of an organosilicon compound having a SiH group and a terminal hydrolyzable group on the molecule. In this example, an organosilicon compound having two or more SiH groups on the molecule and no terminal hydrolyzable group is used as the organosilicon compound. Here, as in the aforementioned method, the fluorooxyalkylene-containing polymer having at least three olefin positions on both ends of the molecular chain and the molecule having two or more SiH groups and no end The organosilicon compound with hydrolyzable groups reacts, and then the polymer with terminal SiH group is obtained as the reaction product and the organosilicon compound with olefin position and terminal hydrolyzable group in the molecule (such as allyl trimethyl) Oxysilane) in the presence of a hydrosilation catalyst (such as a toluene solution of chloroplatinic acid/vinylsiloxane complex) at 40 to 120°C, preferably 60 to 100°C, and more preferably It is aged at a temperature of about 80°C for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours.

The fluorooxyalkylene polymer having at least three olefin positions on both ends of the molecular chain is generally a fluorooxyalkylene polymer of the following general formula (13).

在此，Rf、Z、V和b係如下文所定義。

Here, Rf, Z, V, and b are as defined below.

Preferred examples of the fluorooxyalkylene-containing polymer of the general formula (13) are shown below. The repeating number (degree of polymerization) of each type of repeating unit constituting the fluorooxyalkylene group in each formula may be any number that satisfies Rf of formula (3).

在此，p1、q1及總和p1+q1係如上文所定義。

Here, p1, q1, and the sum p1+q1 are as defined above.

The fluorooxyalkylene-containing polymer of formula (13) can be prepared by, for example, mixing a fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain with an olefin introduction compound, and mixing the mixture In the presence of a base and optional additives or solvents for improving reactivity, at a temperature of 0 to 90°C, preferably 60 to 80°C, and more preferably about 70°C, for 1 to 25 hours, preferably 3 to 10 hours, and more preferably about 6 hours of aging.

In another method for preparing the fluorooxyalkylene-containing polymer of formula (13), the dehydrogenation reaction is a combination of a fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain and an olefin-containing polymer Between hydrogen silane or hydrogen siloxane in the presence of a dehydrogenation catalyst and optionally a solvent, at a temperature of 0 to 60°C, preferably 15 to 35°C, and more preferably about 25°C To 24 hours Time, preferably 30 minutes to 2 hours, and more preferably about 1 hour.

Examples of the fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain that can be used to prepare the fluorooxyalkylene-containing polymer of formula (13) include those shown below.

在此，p1、q1及總和p1+q1係如上文所定義。

Here, p1, q1, and the sum p1+q1 are as defined above.

The fluorine-containing oxyalkylene polymer having hydroxyl groups on both ends of the molecular chain can be prepared, for example, by the following method: wherein there will be fluorine groups (-C(=O)-F on both ends of the molecular chain) ) Perfluorooxyalkylene-containing polymer is mixed with a nucleophilic reagent and a solvent (such as 1,3-bis(trifluoromethyl)benzene or tetrahydrofuran), and the temperature is 0 to 80°C , Preferably 50 to 70°C, and more preferably about 60°C for 1 to 6 hours, preferably 3 to 5 hours, and more preferably about 4 hours of aging.

In addition to the above-mentioned fluorine, other groups can also be used as groups on both ends of the molecular chain in the perfluoroalkylene oxide-containing polymer, such as halides, acid anhydrides, esters, carboxylic acids and amides.

Examples of perfluorooxyalkylene-containing polymers having these groups at both ends of the molecular chain are shown below.

在此，p1、q1及總和p1+q1係如上文所定義。

Here, p1, q1, and the sum p1+q1 are as defined above.

Examples of nucleophilic reagents that can be used to prepare fluorooxyalkylene-containing polymers having hydroxyl groups at both ends of the molecular chain include allyl magnesium halide, 3-butenyl magnesium halide, and 4-pentene halide Base magnesium and 5-hexenyl magnesium halide. It is also possible to use the corresponding lithium reagent.

The amount of the nucleophilic agent used may be 4 to 10 equivalents per equivalent of reactive end groups on the perfluorooxyalkylene-containing polymer, more preferably 5 to 7 equivalents, and even more preferably about 6 equivalents.

Examples of solvents that can be used to prepare fluorooxyalkylene-containing polymers having hydroxyl groups at both ends of the molecular chain include the following fluorocarbon solvents: 1,3-bis(trifluoromethyl)benzene, trifluoromethane Benzene, Hydrofluoroether (HFE) solvents (Novec series obtained from 3M Co.) (such as methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl Ether and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane), and are derived from fully fluorinated compounds Composition of perfluorinated solvent (Fluorinert series obtained from 3M Co.). Other organic solvents that can be used include ether solvents such as tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxins. alkyl.

The amount of the solvent used may be 10 to 300 parts by weight per 100 parts by weight of the fluorooxyalkylene-containing polymer, preferably 100 to 200 parts by weight, and more preferably about 150 parts by weight.

Next, the reaction was stopped and the reaction mixture was separated into a water layer and a fluorocarbon solvent layer by a liquid separation operation. The fluorocarbon solvent layer thus obtained is washed with an organic solvent and the solvent is removed by distillation to give a fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain.

Examples of olefin-introducing compounds that can be used to prepare the fluorooxyalkylene-containing polymer of formula (13) include allyl halides such as allyl chloride, allyl bromide, and allyl iodide, and also include 4- Chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 5-chloro-1-pentene, 5-bromo-1-pentene and 5-iodo-1-pentene Ene.

The amount of olefin-introducing compound used can be per equivalent of reactive ends on the fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain The group is preferably 1 to 10 equivalents, more preferably 2.5 to 6 equivalents, and even more preferably about 5 equivalents.

The base series that can be used to prepare the fluorooxyalkylene-containing polymer of formula (13) are exemplified by amines and alkali metal bases. Examples of amines include triethylamine, diisopropylethylamine, pyridine, DBU, and imidazole. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, potassium tertiary butoxide, lithium diisopropylamide, lithium bis(trimethylsilyl)amide , Bis(trimethylsilyl) sodium and bis(trimethylsilyl) potassium.

The amount of the base used may be 1 to 10 equivalents, more preferably 4 to 6 equivalents per equivalent of reactive end groups on the fluorooxyalkyl group-containing polymer having hydroxyl groups on both ends of the molecular chain, and It is even more preferably about 5 equivalents.

When preparing the fluorooxyalkylene-containing polymer of formula (13), tetrabutylammonium halide, alkali metal halide, and the like can be used as additives to increase reactivity. Examples of such additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, and crown ether. These additives increase reactivity by catalytic halogen exchange with olefin-introduced compounds in the reaction system, and crown ethers increase reactivity by coordination with metals.

The amount of these additives used may be 0.005 to 0.1 equivalents per equivalent of reactive end groups on the fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain, more preferably 0.01 to 0.05 The equivalent, and even more preferably about 0.02 equivalent.

The fluorooxyalkylene-containing polymer of formula (13) can be prepared using a solvent. The use of solvents is not absolutely necessary, but examples of solvents that can be used include the following fluorocarbon solvents: fluorine-containing aromatic hydrocarbon solvents (such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene) , Hydrofluoroether (HFE) solvent (Novec series obtained from 3M Co.) (such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2 -(Trifluoromethyl)pentane), and perfluorinated solvents composed of fully fluorinated compounds (Fluorinert series obtained from 3M Co.). In addition, usable organic solvents include dimethylformamide, dimethylacetamide, dimethyl sulfenium, acetonitrile, and THF.

When a solvent is used, the amount of the solvent used can be from 10 to 300 parts by weight, preferably 30 to 150 parts by weight per 100 parts by weight of the fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain. Parts by weight, and more preferably about 50 parts by weight.

Examples of olefin-containing hydrosiloxanes and hydrosiloxanes that can be used to prepare the fluorooxyalkylene-containing polymer of formula (13) include hydrosiloxanes such as dimethylvinylsilane, dimethylallylsilane, Diethyl vinyl silane and diethyl allyl silane; and hydrosiloxanes, such as vinyl tetramethyl disiloxane, allyl tetramethyl disiloxane, vinyl tetraethyl disilane Oxyane, allyl tetraethyl disiloxane, vinyl tetraphenyl disiloxane, allyl tetraphenyl disiloxane, vinyl hexamethyl trisiloxane and allyl hexamethyl基TRIsiloxane.

The usage amount of the olefin-containing hydrosiloxane or hydrosiloxane may be 1 to 5 equivalents per equivalent of reactive end groups on the fluorooxyalkylene polymer having hydroxyl groups on both ends of the molecular chain , More preferably 1.5 to 3 equivalents, and even more preferably about 2 equivalents.

The dehydrogenation catalysts that can be used to prepare the fluorooxyalkylene-containing polymer of formula (13) are based on rhodium, palladium, ruthenium and other platinum group metals, and boron catalysts are examples. Examples include catalysts based on platinum group metals, such as palladium (triphenylphosphine) and chloroginseng (triphenylphosphine) rhodium, and boron catalysts, such as ginseng (pentafluorophenyl)borane.

The amount of the dehydrogenation catalyst used may be 0.01 to 0.0005 equivalents per equivalent of reactive end groups on the fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain, more preferably 0.007 to 0.001 equivalent, and even more preferably about 0.005 equivalent.

Next, the reaction was stopped and the reaction mixture was separated into a water layer and a fluorocarbon solvent layer by a liquid separation operation. The fluorocarbon solvent layer thus obtained is washed with an organic solvent and the solvent is removed by distillation to give the fluorooxyalkylene-containing polymer of formula (13).

In preparing the polymer-modified silane of the fluoropolyether of formula (1) in which α is 2, the solvent used is preferably a fluorocarbon solvent. Illustrative examples of fluorocarbon solvents include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, hydrofluoroether (HFE) solvents (Novec series obtained from 3M Co.) (such as methyl nonafluoromethyl) Butyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether and 1,1,1,2,3,4,4,5,5,5-decafluoro-3 -Methoxy-2-(trifluoromethyl)pentane), and a perfluorinated solvent composed of fully fluorinated compounds (Fluorinert series obtained from 3M Co.).

The solvent can be used in an amount of 10 to 300 parts by weight per 100 parts by weight of perfluorooxyalkylene-containing polymer having three or more olefin positions on both ends of the molecular chain, preferably 50 to 150 parts by weight, and more It is preferably about 100 parts by weight.

In the preparation of polymer-modified silanes of fluorine-containing polyether of formula (1) in which α is 2, the organosilicon compound having SiH group and terminal hydrolyzable group in the molecule is preferably the following general formula (5) To the compound of any one of (8).

在此，R、X、n、R¹、R²、R³、g、i和j係如上文所定義。

Here, R, X, n, R ¹ , R ² , R ³ , g, i, and j are as defined above.

Examples of these organosilicon compounds having SiH groups and terminal hydrolyzable groups on the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxy Silane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and silanes such as the following.

In the preparation of polymer-modified silanes of fluorine-containing polyether of formula (1) in which α is 2, when the fluorine-containing oxyalkylene group has three or more olefin positions on both ends of the molecular chain, When the polymer reacts with organosilicon compounds with SiH groups and terminal hydrolyzable groups on the molecule, the usage amount of the organosilicon compounds with SiH groups and terminal hydrolyzable groups on the molecule is such that The fluorooxyalkylene-containing polymer having three or more olefin positions on both ends preferably has 3 to 9 equivalents per equivalent of reactive end groups, more preferably 5 to 7 equivalents, and even more It is preferably about 6 equivalents.

In the preparation of polymer-modified silanes of fluorine-containing polyether of formula (1) where α is 2, organosilicon compounds having two or more SiH groups and no terminal hydrolyzable groups are preferred It is a compound of any one of the following general formulas (9) to (11).

Here, R ¹ , R ² , g, j, and i are as defined above.

Examples of organosilicon compounds having two or more SiH groups on the molecule and no terminal hydrolyzable groups include those shown below.

In the preparation of polymer-modified silanes of fluorine-containing polyether of formula (1) in which α is 2, when the fluorine-containing oxyalkylene group has three or more olefin positions on both ends of the molecular chain, When the polymer is reacted with an organosilicon compound with two or more SiH groups and no terminal hydrolyzable groups on the molecule, it has two or more SiH groups on the molecule and no terminal water The usage amount of the group-dissolving organosilicon compound is preferably based on each equivalent of reactive end groups on the fluorooxyalkylene-containing polymer having three or more olefin positions on both ends of the molecular chain It is 7 to 30 equivalents, more preferably 10 to 20 equivalents, and even more preferably about 15 equivalents.

In the preparation of polymer-modified silanes of fluorine-containing polyether of formula (1) in which α is 2, the organosilicon compound having olefin positions and terminal hydrolyzable groups on the molecule is preferably the following general formula (12) Compound.

在此，R、X、U和n係如上文所定義。

Here, R, X, U, and n are as defined above.

In the preparation of polymer-modified silanes of fluoropolyether of formula (1) where α is 2, when the organosilicon compound with olefin position and terminal hydrolyzable group on the molecule is When the reaction product of a polymer containing three or more olefin positions of fluorine-containing oxygen alkylene and an organosilicon compound having two or more SiH groups and no terminal hydrolyzable group on the molecule react, The amount of the organosilicon compound with olefin positions and terminal hydrolyzable groups on the molecule is based on the fluorine-containing oxygen alkylene polymer having three or more olefin positions on the two ends of the molecular chain and The reaction product of an organosilicon compound having two or more SiH groups and no terminal hydrolyzable group on the molecule preferably has 3 to 9 equivalents, more preferably 5 to 7 equivalents, per equivalent of reactive end groups, And even more preferably about 6 equivalents.

In the preparation of polymer-modified silane of fluorine-containing polyether of formula (1) where α is 2, the hydrosilation catalyst is a catalyst with platinum group metals as the substrate (various Such as platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and compounds such as olefins, aldehydes, vinyl silicone or acetylene alcohol), four (triphenylphosphine) palladium and chloroginseng (three Phenylphosphine) rhodium is an example. Platinum compounds are preferred, such as vinylsiloxane coordination compounds.

The usage amount of the hydrosilation catalyst with transition metal as the substrate is relative to the fluorooxyalkylene-containing polymer having three or more olefin positions on the two ends of the molecular chain and the polymer having two The weight of the reaction product of or more SiH groups and an organosilicon compound without terminal hydrolyzable groups is preferably 0.1 to 100 ppm, and more preferably 1 to 50 ppm.

The target compound can then be obtained by distilling off the solvent and unreacted reagents under reduced pressure.

作為在分子鏈之兩個末端上分別具有三或更多個烯烴位置的含氟氧伸烷基之聚合物及使用三甲氧基矽烷作為在分子上具有SiH基團及末端可水解基團之有機矽化合物可獲得下式化合物。 For example, by using a compound of the formula

As a polymer of fluorine-containing oxygen alkylene having three or more olefin positions on both ends of the molecular chain and using trimethoxysilane as an organic molecule having SiH groups and terminal hydrolyzable groups The silicon compound can obtain the compound of the following formula.

The present invention further provides a surface treatment agent, which includes the above-mentioned fluorine-containing polyether polymer modified silane. The surface treatment agent may include the hydroxyl groups on the silane modified by condensation on the fluorine-containing polyether polymer, or the terminal hydrolyzable groups on the silane modified by the fluoropolyether polymer modified by condensation in advance using a known method A partial (hydrolyzed) condensate obtained by the partial hydrolysis of the hydroxyl group formed by the group.

When necessary, a hydrolysis/condensation catalyst can be added to the surface treatment agent. Examples of such catalysts include organotin compounds (e.g. dibutyltin dimethoxide, dibutyltin dilaurate), organic titanium compounds (e.g. tetra-n-butyl titanate), organic acids (e.g. acetic acid, methanesulfonic acid, fluorine Carboxylic acids) and inorganic acids (e.g. hydrochloric acid, sulfuric acid). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate and fluorine-modified carboxylic acid are particularly preferred.

The amount of hydrolysis/condensation catalyst added per 100 parts by weight of fluoropolyether polymer-modified silane and/or its partial (hydrolysis) condensate is usually 0.01 to 5 parts by weight, and is preferably 0.1 to 1 part by weight.

The surface treatment agent may include a suitable solvent. Examples of these solvents include fluorine-modified aliphatic hydrocarbon solvents (e.g. perfluoroheptane, perfluorooctane), fluorine-modified aromatic hydrocarbon solvents (e.g. 1,3-bis(trifluoromethyl)benzene) , Fluorine-modified ether solvents (such as methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran)), fluorine-modified alkylamine solvents (such as perfluorotributylamine) , Perfluorotriphenylamine), hydrocarbon solvents (such as petroleum essence, toluene, xylene), and ketone solvents (such as acetone, methyl ethyl ketone, methyl isobutyl ketone). Among them, in terms of properties such as solubility and wettability, 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), all Fluorotributylamine and ethyl perfluorobutyl ether are particularly preferred.

Two or more of these solvents can be mixed and used, and it is preferable to uniformly dissolve the fluorine-containing polyether polymer modified silane and its partial (hydrolysis) condensate therein. The optimized concentration of the polymer-modified silane and its partial (hydrolyzed) condensate dissolved in the solvent of the fluorine-containing polyether varies with the processing method and should be a quantity that is easy to weigh. The concentration used for direct administration is preferably 0.01 to 10 parts by weight per 100 parts by weight of the combined amount of solvent and polymer-modified silane (and its partial (hydrolysis) condensate) containing fluoropolyether, and especially 0.05 to 5 parts by weight. The concentration used for the vapor deposition treatment is preferably 1 to 100 parts by weight per 100 parts by weight of the combined amount of the solvent and the polymer-modified silane (and its partial (hydrolysis) condensate) of the fluoropolyether, and especially 3 to 30 parts by weight.

The surface treatment agent of the present invention can be applied to the substrate by generally known methods, such as brushing, dipping, spraying or vapor deposition. The heating method used during the vapor deposition process may be resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies with the curing method. For example, curing for direct application (such as brushing, dipping, spraying) is performed at a temperature of 25 to 200°C, and especially 25 to 80°C, for 30 minutes to 36 hours, and especially 1 to 24 hours. good. The curing temperature for application by vapor deposition is desirably in the range of 20 to 200°C. It is also possible to cure in humid conditions. The thickness of the cured film is appropriately selected according to the substrate type, but is usually from 0.1 to 100 nanometers, and particularly from 1 to 20 nanometers. In the spraying example, the surface treatment agent is diluted with a fluorocarbon solvent that has been added with some water in advance to complete the hydrolysis (that is, to form Si-OH groups) and The surface treatment agent is then sprayed on the substrate, resulting in rapid curing after application.

The substrate to be treated with the surface treatment agent of the present invention is not particularly limited and can be made of any of various types of materials, such as paper, fabric, metal and its oxide, glass, plastic, ceramic or quartz. It is particularly preferable to use a surface treatment agent on the SiO ₂ treated glass or film.

Objects that can be treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, digital cameras, digital cameras, PDAs, portable players, car audio systems, game consoles, optical objects (such as glasses lenses, camera lenses) , Filter lenses and sunglasses), medical devices (such as gastroscopes), photocopiers, personal computers, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films and anti-reflective coatings. The surface treatment agent of the present invention is particularly used as a water-repellent/oil-repellent layer on touch panel displays and anti-reflection films, because it prevents fingerprints and sebum from being left on these objects and can also impart abrasion resistance and scratch resistance Hurtful.

The surface treatment agent of the present invention is also used as an anti-fouling coating for sanitary facilities (such as bathtubs and water tanks); a sludge-resistant coating for window glass, tempered glass, headlight covers and the like in automobiles, trams and aircraft ; Water-repellent/oil-repellent coating for building materials used in outdoor walls; Water-repellent/oil-repellent coating for building materials in kitchens; no dirt, labels/posters and graffiti attached to the coating of telephone booths; no fingerprints attached Coating on process parts; coating that does not make fingerprints adhere to discs and DVDs; mold lubricants; paint additives; resin modifiers; flow modifiers or dispersion modifiers for inert fillers; and Lubricity enhancer for tapes and films.

Example

The operation examples and comparative examples of the present invention are presented below by way of illustration and not limitation.

Example 1

50克(4.2×10^-1莫耳)烯丙基溴及0.6克(1.7×10^-3莫耳)碘化四丁基銨。接下來添加23克(4.2×10^-1莫耳)氫氧化鉀，隨後將混合物在70℃下加熱6小時。在完成加熱之後，將系統冷卻至室溫且逐滴添加水性氫氯酸溶液。將底部的氟碳化合物層以分液操作回收且以丙酮清洗。再回收在清洗之後於底部的氟碳化合物層且將剩餘溶劑在減壓下以蒸餾驅除。再進行上述操作以給出270克下式(B)的含氟聚醚之聚合物。 Mix the following together in the reactor: 300 g (8.3×10 ^-2 mol) of the compound of the following formula (A)

50 g (4.2×10 ^-1 mol) allyl bromide and 0.6 g (1.7×10 ^-3 mol) tetrabutylammonium iodide. Next, 23 g (4.2×10 ⁻¹ mol) of potassium hydroxide was added, and then the mixture was heated at 70° C. for 6 hours. After the heating is completed, the system is cooled to room temperature and the aqueous hydrochloric acid solution is added dropwise. The fluorocarbon layer at the bottom was recovered in a liquid separation operation and washed with acetone. The fluorocarbon layer at the bottom after cleaning is recovered and the remaining solvent is distilled away under reduced pressure. The above operation was performed to give 270 g of the polymer of fluorine-containing polyether of the following formula (B).

¹ H-NMR δ 2.4-2.6(CC H ₂ CH=CH ₂ )4H δ 4.0-4.1(OC H ₂ CH=CH ₂ )2H δ 4.9-5.2(-CH ₂ CH=C H ₂ )6H δ 5.7- 5.9(C-CH ₂ C H =CH ₂ )3H

200克1,3-雙(三氟甲基)苯、40克(3.3×10^-1莫耳)三甲氧基矽烷及氯鉑酸/乙烯基矽氧烷複合物之2.0×10^-1克甲苯溶液(含有6.0×10^-7莫耳Pt)，且將混合物在80℃下經24小時老化。接著將溶劑及未反應之試劑在減壓下以蒸餾移除，以給出210克液體產物。 Mix the following together in the reactor: 200 g (5.5×10 ^-2 mol) of the compound of formula (B) obtained above

200 g of 1,3-bis(trifluoromethyl)benzene, 40 g (3.3×10 ^-1 mol) of trimethoxysilane, and 2.0×10 ^-1 g of toluene of chloroplatinic acid/vinylsiloxane compound Solution (containing 6.0×10 ⁻⁷ mol Pt), and the mixture was aged at 80° C. for 24 hours. Then, the solvent and unreacted reagents were removed by distillation under reduced pressure to give 210 g of liquid product.

The obtained compound was analyzed by NMR and had the structure shown in the following formula (C).

¹ H-NMR δ 0.5-0.7(-CH ₂ CH ₂ C H ₂ -Si)6H δ 1.4-1.9(-C H ₂ C H ₂ CH ₂ -Si)12H δ 3.3-3.7(-Si(OC H ₃ ) ₃ )27H

Example 2

Mix the following together in the reactor: 100 grams of 1,3-bis(trifluoromethyl)benzene, 0.028 grams (5.4×10 ^-4 mol) of ginseng (pentafluorophenyl) borane and 100 grams ( 2.7×10 ^-2 mol) The compound of the following formula (A).

接下來慢慢地逐滴添加3.8克(3.8×10^-2莫耳)二甲基烯丙基矽烷，隨後將混合物在25℃加熱1小時。在這之後逐滴添加水，隨後將底部的氟碳化合物層以分液操作回收且以丙酮清洗。再回收在清洗之後於底部的氟碳化合物層且將剩餘溶劑在減壓下以蒸餾驅除，以給出95克下式(D)的含氟聚醚之聚合物。

Next, 3.8 g (3.8×10 ⁻² mol) of dimethylallylsilane was slowly added dropwise, and then the mixture was heated at 25° C. for 1 hour. After that, water was added dropwise, and then the fluorocarbon layer at the bottom was recovered in a liquid separation operation and washed with acetone. The fluorocarbon layer at the bottom after cleaning was recovered and the remaining solvent was distilled off under reduced pressure to give 95 g of the fluoropolyether polymer of the following formula (D).

¹ H-NMR δ 0-0.2(-Si-C H ₃ ) ₂ -)6H δ 1.5-1.7(-Si-CH ₃ ) ₂ -C H ₂ -)2H δ 2.3-2.6(-C H ₂ CH= CH ₂ )4H δ 4.7-5.2(-CH ₂ CH=C H ₂ )6H δ 5.7-5.9(-CH ₂ C H =CH ₂ )3H

90克1,3-雙(三氟甲基)苯、三甲氧基矽烷及9.5×10^-1克氯鉑酸/乙烯基矽氧烷複合物之18克(1.5×10^-1莫耳)甲苯溶液(含有2.9×10^-7莫耳Pt)，且將混合物在80℃下經24小時老化。將溶劑及未反應之試劑在減壓下以蒸餾移除，以給出95克液體產物。 Mix the following together in the reactor: 90 g (2.4×10 ^-2 mol) of the compound of formula (D) obtained above

90 grams of 1,3-bis(trifluoromethyl)benzene, trimethoxysilane and 9.5×10 ^-1 gram of chloroplatinic acid/vinylsiloxane compound 18 grams (1.5×10 ^-1 mol) toluene Solution (containing 2.9×10 ⁻⁷ mol Pt), and the mixture was aged at 80° C. for 24 hours. The solvent and unreacted reagents were removed by distillation under reduced pressure to give 95 g of liquid product.

The obtained compound was analyzed by NMR and had the structure shown in the following formula (E).

¹ H-NMR δ 0-0.3(-Si-C H ₃ ) ₂ -)6H δ 0.5-0.8(-Si-CH ₃ ) ₂ -C H ₂ CH ₂ C H ₂ -Si,C-CH ₂ CH ₂ C H ₂ -Si)8H δ 1.3-1.9(-Si-CH ₃ ) ₂ -CH ₂ C H ₂ CH ₂ -Si,CC H ₂ C H ₂ CH ₂ -Si) 10H δ 3.3-3.7(-Si( OC H ₃ ) ₃ )27H

Example 3

Mix the following together in the reactor: 100 grams of 1,3-bis(trifluoromethyl)benzene, 0.028 grams (5.4×10 ^-4 mol) of ginseng (pentafluorophenyl) borane and 100 grams ( 2.7×10 ^-2 mol) The compound of the following formula (A).

接下來慢慢地逐滴添加6.5克(5.4×10^-2莫耳)二甲基乙烯基矽烷，隨後將混合物在25℃下加熱1小時。在這之後逐滴添加水，隨後將底部的氟碳化合物層以分液操作回收且以丙酮清洗。再回收在清洗之後於底部的氟碳化合物層且將剩餘溶劑在減壓下以蒸餾驅除，以給出99克下式(F)的含氟聚醚之聚合物。

Next, 6.5 g (5.4×10 ⁻² mol) of dimethyl vinyl silane was slowly added dropwise, and then the mixture was heated at 25° C. for 1 hour. After that, water was added dropwise, and then the fluorocarbon layer at the bottom was recovered in a liquid separation operation and washed with acetone. The fluorocarbon layer at the bottom after cleaning was recovered and the remaining solvent was distilled away under reduced pressure to give 99 g of the fluoropolyether polymer of the following formula (F).

¹ H-NMR δ 0-0.2(-Si-C H ₃ ) ₂ -)6H δ 2.4-2.5(-C H ₂ CH=CH ₂ )4H δ 4.7-5.2(-CH ₂ CH=C H ₂ )4H δ 5.6-6.2(-CH ₂ C H =CH ₂ ,-Si-(CH ₃ ) ₂ -C H =C H ₂ )5H

90克1,3-雙(三氟甲基)苯、18克(1.5×10^-1莫耳)三甲氧基矽烷及氯鉑酸/乙烯基矽氧烷複合物之9.5×10^-1克甲苯溶液(含有2.9×10^-7莫耳Pt)，且將混合物在80℃下經24小時老化。將溶劑及未反應之試劑在減壓下以蒸餾移除，以給出97克液體產物。 Mix the following together in the reactor: 90 g (2.4×10 ^-2 mol) of the compound of formula (F) obtained above

90 g 1,3-bis(trifluoromethyl)benzene, 18 g (1.5×10 ^-1 mol) trimethoxysilane and 9.5×10 ^-1 g toluene of chloroplatinic acid/vinylsiloxane compound Solution (containing 2.9×10 ⁻⁷ mol Pt), and the mixture was aged at 80° C. for 24 hours. The solvent and unreacted reagents were removed by distillation under reduced pressure to give 97 g of liquid product.

The obtained compound was analyzed by NMR and had the structure shown in the following formula (G).

¹ H-NMR δ 0-0.3(-Si-C H ₃ ) ₂ -)6H δ 0.5-0.8(-Si-CH ₃ ) ₂ -C H ₂ C H ₂ -Si,C-CH ₂ CH ₂ C H ₂ -Si)8H δ 1.4-2.0(CC H ₂ C H ₂ CH ₂ -Si)8H δ 3.4-3.7(-Si(OC H ₃ ) ₃ )27H

Example 4

Mix the following together in the reactor: 100 grams of 1,3-bis(trifluoromethyl)benzene, 0.028 grams (5.4×10 ^-4 mol) of ginseng (pentafluorophenyl) borane and 100 grams ( 2.7×10 ^-2 mol) The compound of the following formula (A).

接下來慢慢地逐滴添加6.4克(4.1×10^-2莫耳)乙烯基四甲基二矽氧烷，隨後將混合物在25℃下加熱1小時。在這之後逐滴添加水，隨後將底部的氟碳化合物層以分液操作回收且以丙酮清洗。再回收在清洗之後於底部的氟碳化合物層且將剩餘溶劑在減壓下以蒸餾驅除，以給出103克下式(H)的含氟聚醚之聚合物。

Next, 6.4 g (4.1×10 ⁻² mol) of vinyl tetramethyl disiloxane was slowly added dropwise, and then the mixture was heated at 25° C. for 1 hour. After that, water was added dropwise, and then the fluorocarbon layer at the bottom was recovered in a liquid separation operation and washed with acetone. The fluorocarbon layer at the bottom after cleaning was recovered and the remaining solvent was distilled away under reduced pressure to give 103 g of the fluoropolyether polymer of the following formula (H).

¹ H-NMR δ 0-0.2(-Si-C H ₃ ) ₂ -)12H δ 2.3-2.5(-C H ₂ CH=CH ₂ )4H δ 4.8-5.0(-CH ₂ CH=C H ₂ )4H δ 5.5-6.1(-CH ₂ C H =CH ₂ ,-Si-(CH ₃ ) ₂ -C H =C H ₂ )5H

90克1,3-雙(三氟甲基)苯、18克(1.5×10^-1莫耳)三甲氧基矽烷及氯鉑酸/乙烯基矽氧烷複合物之9.5×10^-1克甲苯溶液(含有2.9×10^-7莫耳Pt)，且將混合物在80℃下經24小時老化。將溶劑及未反應之試劑在減壓下以蒸餾移除，以給出96克液體產物。 Mix the following together in the reactor: 90 g (2.4×10 ^-2 mol) of the compound of formula (H) obtained above

90 g 1,3-bis(trifluoromethyl)benzene, 18 g (1.5×10 ^-1 mol) trimethoxysilane and 9.5×10 ^-1 g toluene of chloroplatinic acid/vinylsiloxane compound Solution (containing 2.9×10 ⁻⁷ mol Pt), and the mixture was aged at 80° C. for 24 hours. The solvent and unreacted reagents were removed by distillation under reduced pressure to give 96 g of liquid product.

The obtained compound was analyzed by NMR and had the structure shown in the following formula (I).

¹ H-NMR δ 0-0.3(-Si-C H ₃ ) ₂ -)12H δ 0.5-0.8(-Si-CH ₃ ) ₂ -C H ₂ C H ₂ -Si,C-CH ₂ CH ₂ C H ₂ -Si)8H δ 1.4-1.9(CC H ₂ C H ₂ CH ₂ -Si)8H δ 3.3-3.7(-Si(OC H ₃ ) ₃ )27H

Example 5

30克(2.5×10^-1莫耳)烯丙基溴及0.36克(1.0×10^-3莫耳)碘化四丁基銨。接下來添加14克(2.5×10^-1莫耳)氫氧化鉀，隨後將混合物在70℃加熱6小時。在完成加熱之後，將系統冷卻至室溫且逐滴添加氫氯酸水性溶液。將底部的氟碳化合物層以分液操作回收且以丙酮清洗。再回收在清洗之後於底部的氟碳化合物層且將剩餘溶劑在減壓下以蒸餾驅除，以給出98克下式(Y)的含氟聚醚之聚合 物。 Mix the following together in the reactor: 100 g (5.0×10 ^-2 mol) of the compound of the following formula (X)

30 g (2.5×10 ^-1 mol) allyl bromide and 0.36 g (1.0×10 ^-3 mol) tetrabutylammonium iodide. Next, 14 grams (2.5×10 ⁻¹ mol) of potassium hydroxide were added, and the mixture was then heated at 70° C. for 6 hours. After the heating is completed, the system is cooled to room temperature and the aqueous hydrochloric acid solution is added dropwise. The fluorocarbon layer at the bottom was recovered in a liquid separation operation and washed with acetone. The fluorocarbon layer at the bottom after cleaning was recovered and the remaining solvent was distilled away under reduced pressure to give 98 g of the fluoropolyether polymer of the following formula (Y).

¹ H-NMR δ 2.1-2.5(CC H ₂ CH=CH ₂ )4H δ 4.0-4.1(OC H ₂ CH=CH ₂ )2H δ 4.7-5.1(-CH ₂ CH=C H ₂ )6H δ 5.5- 5.8(-CH ₂ C H =CH ₂ )3H

90克1,3-雙(三氟甲基)苯、17克(1.4×10^-1莫耳)三甲氧基矽烷及氯鉑酸/乙烯基矽氧烷複合物之9.1×10^-1克甲苯溶液(含有2.8×10^-7莫耳Pt)，且將混合物在80℃下經24小時老化。將溶劑及未反應之試劑在減壓下以蒸餾移除，以給出95克液體產物。 Mix the following together in the reactor: 90 g (2.3×10 ^-2 mol) of the compound of formula (Y) obtained above

90 g 1,3-bis(trifluoromethyl)benzene, 17 g (1.4×10 ^-1 mol) trimethoxysilane and 9.1×10 ^-1 g toluene of chloroplatinic acid/vinylsiloxane compound The solution (containing 2.8×10 ⁻⁷ mol Pt), and the mixture was aged at 80° C. for 24 hours. The solvent and unreacted reagents were removed by distillation under reduced pressure to give 95 g of liquid product.

The obtained compound was analyzed by NMR and had the structure shown in the following formula (Z).

¹ H-NMR δ 0.4-0.7(-CH ₂ CH ₂ C H ₂ -Si)6H δ 1.4-1.8(-C H ₂ C H ₂ CH ₂ -Si)12H δ 3.2-3.6(-Si(OC H ₃ ) ₃ )27H

Example 6

91克(7.5×10^-1莫耳)烯丙基溴及1.1克(3.0×10^-3莫耳)碘化四丁基銨。接下來添加42克(7.5×10^-1莫耳)氫氧化鉀，隨後將混合物在70℃下加熱6小時。在完成加熱之後，將系統冷卻至室溫且逐滴添加氫氯酸水性溶液。將底部的氟碳化合物層以分液操作回收且以丙酮清洗。再回收在清洗之後於底部的氟碳化合物層且將剩餘溶劑在減壓下以蒸餾驅除，以給出287克下式(K)的含氟聚醚之聚合物。 Mix the following in the reactor: 300 g (1.5×10 ^-1 mol) of the compound of the following formula (J)

91 g (7.5×10 ^-1 mol) allyl bromide and 1.1 g (3.0×10 ^-3 mol) tetrabutylammonium iodide. Next, 42 g (7.5×10 ⁻¹ mol) of potassium hydroxide was added, and then the mixture was heated at 70° C. for 6 hours. After the heating is completed, the system is cooled to room temperature and the aqueous hydrochloric acid solution is added dropwise. The fluorocarbon layer at the bottom was recovered in a liquid separation operation and washed with acetone. The fluorocarbon layer at the bottom after cleaning was recovered and the remaining solvent was distilled away under reduced pressure to give 287 g of a fluoropolyether polymer of the following formula (K).

43 p1: q1=47:53, p1+q1

43

¹ H-NMR δ 2.4-2.6(CC H ₂ CH=CH ₂ )8H δ 4.0-4.1(OC H ₂ CH=CH ₂ )4H δ 4.9-5.2(-CH ₂ CH=C H ₂ )12H δ 5.7-5.9(-CH ₂ C H =CH ₂ )6H

Mix the following together in the reactor: 200 g (1.0×10 ^-1 mol) of the compound of formula (K) obtained above

43 200克1,3-雙(三氟甲基)苯、73克(6.0×10^-1莫耳)三甲氧基矽烷及氯鉑酸/乙烯基矽氧烷複合物之3.6×10^-1克甲苯溶液(含有1.1×10^-6莫耳Pt)，且將混合物在80℃下經24小時老化。將溶劑及未反應之試劑在減壓下以蒸餾移除，以給出206克液體產物。 p1: q1=47:53, p1+q1

43 200 g of 1,3-bis(trifluoromethyl)benzene, 73 g (6.0×10 ^-1 mol) of trimethoxysilane, and 3.6×10 ^-1 g of chloroplatinic acid/vinylsiloxane compound Toluene solution (containing 1.1×10 ⁻⁶ mol Pt), and the mixture was aged at 80° C. for 24 hours. The solvent and unreacted reagents were removed by distillation under reduced pressure to give 206 g of liquid product.

The obtained compound was analyzed by NMR and had the structure shown in the following formula (L).

43 p1: q1=47:53, p1+q1

43

¹ H-NMR δ 0.5-0.7(-CH ₂ CH ₂ C H ₂ -Si)12H δ 1.4-1.9(-C H ₂ C H ₂ CH ₂ -Si)24H δ 3.3-3.7(-Si(OC H ₃ ) ₃ )54H

The following polymers were used as comparative examples.

Comparative Example 1

CF ₃ O-(CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -O-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ (M)

43 p1: q1=47:53, p1+q1

43

Comparative Example 2

43 (N) (H ₃ CO) ₃ Si-CH ₂ CH ₂ CH ₂ -OCH ₂ -CF ₂ O-(CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -CH ₂ O-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ p1: q1=47: 53, p1+q1

43 (N)

Comparative Example 3

Preparation of surface treatment agent and formation of cured film

The polymer-modified silane of fluorine-containing polyether obtained in Examples 1 to 6 and the polymers of Comparative Examples 1 to 3 were dissolved in Novec 7200 (ethyl perfluorobutyl ether from 3M Co.) to become With a concentration of 0.1% by weight, the surface treatment agent was prepared. Spray each surface treatment agent (treatment conditions: operating speed 360 mm/sec; feeding pitch 12 mm) on the glass (Gorilla® glass 3 from Corning Inc.) to a coating of 8.5×10 ^-3 /m² It is cured at 25°C and 40% humidity for 24 hours to form a cured film with a thickness of 8nm.

Evaluation of water repellency/oil repellency

Evaluation of initial water repellency/oil repellency:

The glass sample prepared above with a cured film formed on its surface was tested using a DropMaster contact angle meter (Kyowa Interface Science Co., Ltd.), and the contact angle of the cured film with water was measured under the following conditions. Aqueous): droplet size 2 microns; temperature 25°C; humidity 40%. The results (initial contact angle with water) are shown in Table 1.

In both the embodiments of the present invention and the comparative Good water repellency.

Evaluation of abrasion resistance:

To test the glass sample prepared above with a cured film formed on its surface, rub the cured film 3,000 times with a friction tester (Shinto Scientific Co., Ltd.) under the conditions shown below. The method measures the contact angle of the cured film with water, and evaluates the wear resistance based on this. The test environment conditions are 25°C and 40% humidity. The results (contact angle with water after abrasion) are shown in Table 1.

Wear resistance to steel wool:

Steel wool: BONSTAR #0000(Nihon Steel Wool Co.,Ltd.)

Contact surface area: 10 mm diameter

Stroke (one way): 30 cm

Travel speed: 1,800/min

Load: 1 kg/cm²

The compounds of Examples 1 to 6 have 3 to 6 reactive functional groups on the molecule, which have more functional groups than the compounds of Comparative Examples 1 to 3. Therefore, even after rubbing with steel wool, the cured film of the surface treatment agent containing the compounds of Examples 1 to 6 has a contact angle with water greater than 100° and therefore exhibits good abrasion resistance.

Japanese Patent Application No. 2015-085708 is incorporated herein for reference.

Although some preferred implementation aspects have been described, many modifications and changes can be made to them according to the above teachings. Therefore, it should be understood that the present invention can be implemented in other ways than the specific description without departing from the scope of the appended patent application.

Claims (9)

A fluorine-containing polyether polymer modified silane with general formula (1):

Where α is 1, and Rf is a polymer residue containing a monovalent fluorooxyalkyl group, which is a part of the general formula (2): F-(CF ₂ O) _p -(C ₂ F ₄ O) _q -(C ₃ F ₆ O) _r -(C ₄ F ₈ O) _s -C _d F _2d- (2) where p is an integer from 5 to 100, q is an integer from 5 to 100, and r is from 0 to 100 Integer, s is an integer from 0 to 100, and the sum is p+q+r+s=10 to 105. Each repeating unit can be linear or branched, and individual repeating units can be arranged arbitrarily, d is from 1 to An integer of 3, and the C _d F _2d unit can be linear or branched, Y is a divalent to hexavalent hydrocarbon group that can have silicon atoms and/or siloxane bonds, and W is a hydrocarbon group that can have silicon atoms and/or silicon A divalent to hexavalent hydrocarbon group with an oxane bond, R is independently an alkyl or phenyl group of 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is an integer from 1 to 3, and a is from An integer from 1 to 5, and m is an integer from 1 to 5. A fluorine-containing polyether polymer modified silane with general formula (1):

Where α is 2, and Rf is a polymer residue containing a divalent fluorooxyalkylene group, which is part of the general formula (3): -C _d F _2d -O-(CF ₂ O) _p -(C ₂ F ₄ O) _q -(C ₃ F ₆ O) _r -(C ₄ F ₈ O) _s -C _d F _2d- (3) where p is an integer from 5 to 100 and q is an integer from 5 to 100 , R is an integer from 0 to 100, s is an integer from 0 to 100, and the sum is p+q+r+s=10 to 105. Each repeating unit can be linear or branched, and individual repeating units can be Arbitrary arrangement, d is an integer from 1 to 3, and C _d F _2d units can be linear or branched, Y is a divalent to hexavalent hydrocarbon group that can have silicon atoms and/or siloxane bonds, W is A divalent to hexavalent hydrocarbon group that may have a silicon atom and/or a siloxane bond, R is independently an alkyl group or phenyl group with 1 to 4 carbon atoms, X is independently a hydrolyzable group or a hydrolyzable group, and n is from An integer from 1 to 3, a is an integer from 1 to 5, and m is an integer from 1 to 5. For example, the polymer-modified silane of item 1 or 2 of the scope of patent application, where the sum p+q is 10 to 105, and r=s=0. For example, the polymer-modified silane of item 1 or 2 of the scope of patent application, wherein Y in formula (1) is selected from the group consisting of: alkylene group of 3 to 10 carbon atoms, containing 6 to 8 The alkylene group of 2 to 8 carbon atoms, which is bonded to each other via a C ₁ -C ₄ silylene or C ₆ -C ₁₀ silylene structure, has 2 to 8 carbons A divalent to a tetravalent group of an alkylene group of atoms and a divalent to tetravalent group of an alkylene group having 2 to 10 carbon atoms bonded at the valence position on the divalent to tetravalent organopolysiloxane residue The organopolysiloxane residue is linear and has 2 to 10 silicon atoms or is branched or cyclic and has 3 to 10 silicon atoms. For example, the polymer-modified silane of item 1 or 2 of the scope of patent application, wherein W in formula (1) is selected from the group consisting of: alkylene groups of 2 to 10 carbon atoms, containing 6 to 8 The alkylene group of 2 to 8 carbon atoms, the alkylene group of 2 to 6 carbon atoms containing diorganosilylene group, the alkylene group of 2 to 6 carbon atoms, the alkylene group of C ₁ -C ₄ silylene group or C ₆ -C _{10 A} divalent group of an alkylene having 2 to 8 carbon atoms in which the silylene structure is bonded to each other, and bonding at the valence position on the divalent to tetravalent organopolysiloxane residue The divalent to tetravalent group of alkylene having 2 to 10 carbon atoms, the organopolysiloxane residue is linear and has 2 to 10 silicon atoms or is branched or cyclic and has 3 to 10 silicon atoms. For example, the polymer-modified silane of item 1 or 2 of the scope of patent application, wherein each X in formula (1) is independently selected from the group consisting of Group: hydroxyl group, alkoxy group of 1 to 10 carbon atoms, alkoxy group of 2 to 10 carbon atoms, acyloxy group of 1 to 10 carbon atoms, alkenoxy group of 2 to 10 carbon atoms And halogen groups. For example, the polymer-modified silane of item 1 or 2 of the scope of patent application has any one of the following formulas:

Where p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and the sum p1+q1 is an integer from 10 to 105. A surface treatment agent comprising the polymer-modified silane and/or its partial (hydrolysis) condensate as in the first or second item of the scope of patent application. An object that has been surface-treated with a surface treatment agent as in item 8 of the scope of the patent application.